EP2080503A1 - Matériaux dentaires dotés d'agents de remplissage à surface fonctionnalisée - Google Patents

Matériaux dentaires dotés d'agents de remplissage à surface fonctionnalisée Download PDF

Info

Publication number
EP2080503A1
EP2080503A1 EP08000956A EP08000956A EP2080503A1 EP 2080503 A1 EP2080503 A1 EP 2080503A1 EP 08000956 A EP08000956 A EP 08000956A EP 08000956 A EP08000956 A EP 08000956A EP 2080503 A1 EP2080503 A1 EP 2080503A1
Authority
EP
European Patent Office
Prior art keywords
filler
groups
formula
carbon atoms
functionalized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08000956A
Other languages
German (de)
English (en)
Other versions
EP2080503B1 (fr
Inventor
Norbert Prof. Dr. Moszner
Jörg Dr. Angermann
Simone Dr. Klapdohr
Volker Dr. Rheinberger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ivoclar Vivadent AG
Original Assignee
Ivoclar Vivadent AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ivoclar Vivadent AG filed Critical Ivoclar Vivadent AG
Priority to EP08000956A priority Critical patent/EP2080503B1/fr
Priority to AT08000956T priority patent/ATE524154T1/de
Priority to US12/275,700 priority patent/US20090186960A1/en
Priority to JP2008334466A priority patent/JP5308809B2/ja
Publication of EP2080503A1 publication Critical patent/EP2080503A1/fr
Application granted granted Critical
Publication of EP2080503B1 publication Critical patent/EP2080503B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/76—Fillers comprising silicon-containing compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/17—Particle size
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A61K6/896—Polyorganosilicon compounds

Definitions

  • the present invention relates to compositions based on surface-functionalized fillers which are particularly suitable as dental materials.
  • the invention also relates to surface-functionalized fillers, to a process for the preparation of the compositions according to the invention and to fillers, and to their use as dental materials for the production of adhesives, coatings or composites.
  • certain acids are also used as reaction components in dental cements, for example, simple acids such as phosphoric acid as a reaction partner for ZnO in phosphate cements, polyacrylic acid as a reaction partner for ZnO in Polycarboxylatzementen, copolymers of acrylic acid and itaconic acid as a reaction partner for calcium aluminosilicate glasses in Glasionomerzementen or certain acid monomers as the reaction component for calcium aluminosilicate glasses in compomers (cf. EC Combe, FJT Burke, WH Douglas, Dental Biomaterials, Kluwer Academic. Publishers, Boston etc. 1999, 211ff., 221ff., 233ff. ; U.Salz, SW Shalaby, Polymers for Dental and Orthopedic Applications, CRC Press, Boca Raton, etc. 2007, 49 ff ).
  • simple acids such as phosphoric acid as a reaction partner for ZnO in phosphate cements, polyacrylic acid as a reaction partner for Zn
  • silicate and non-silicate inorganic fillers are often used, in particular silicate and non-silicate inorganic fillers.
  • ground glasses such as barium silicate glasses ( US 4,220,582 ), Strontium silicate glasses ( DE 43 23 143 ), Lithium aluminum silicate glasses ( GB 1 488 403 ) and X-ray opaque aluminum fluoro-silicate glasses, which are mainly used in methacrylate-reinforced glass ionomers ( US 5,367,002 . US 5,871,360 ).
  • Pure silica fillers are also used in dental materials ( DE 24 05 578 ).
  • mixed oxides based on silicon and zirconium oxide DE 32 47 800 ).
  • Non-silicate fillers are used in particular as X-ray contrast agents, for example zirconium oxide ( WO 00/69392 ), Tantalum oxide ( WO 98/13008 ) or yttrium oxide ( DE 100 18 405 ).
  • Aluminum and titanium oxide serve as opacifiers because of their high refractive index.
  • fillers By modifying their surface different properties of fillers can be adjusted.
  • siliceous fillers for example, a silanization can be carried out for this purpose.
  • UV absorptivity and dirt-repellent properties of fillers and to improve their suspensibility and ability to integrate into a plastic matrix of the DE 10 2004 022 566 A1 discloses a process for coating glass, glass-ceramic and / or ceramic powders in which silanes containing certain functional groups are used as coating reagents.
  • fillers In the dental field, the use of fillers is known whose surfaces are modified with polymerizable groups, so that they are covalently connected by copolymerization in the curing of the material with the polymer matrix (for example, a methacrylate matrix).
  • Silicate fillers can be silanized for this purpose, for example, with prehydrolyzed (meth) acryloxyalkyltrialkoxysilanes (cf., for example, for filling and fixing materials DE 40 29 230 , or for coatings US 2002/0065337 ).
  • Non-silicate fillers such as zirconium oxide can be prepared, for example, by methacrylate-modified polyethercarboxylic acids ( US 6,387,981 ) or (meth) acryloyloxyalkyl dihydrogen phosphate ( US 6,417,244 ) are surface modified.
  • Silicate materials surface-functionalized with aldehyde or acid groups are used in molecular biology or affinity chromatography, for example for the immobilization of proteins and polypeptides.
  • the preparation of functionalized with CHO groups SiO 2 particles or SiO 2 nanotubes via a reaction with aldehyd phenomenon inconveniencen silanes, such as trimethoxysilyl butyraldehyde or trimethoxysilylpropionaldehyde (see. MT Dulay et al., Analyt. Chem. 77 (2005) 4604-4610 ; G. MacBeath, SL Schreiber, Science 289 (2000) 1760-1763 ; Clarke, W., et al., J. Chromatography A 2000 (888) 13-22 ; SB Lee et al., Science 296 (2002) 2198-2200 ).
  • the invention has for its object to provide fillers that can be incorporated easily into a variety of resin or polymer matrix systems and are suitable for the production of dental adhesives, cements, composites or coatings, have good mechanical properties and show improved adhesion to the hard tooth substance.
  • linked refers to a chemical bond, preferably a covalent chemical bond.
  • a group can be interrupted by a group such as an ether group is understood to mean that the group is inserted into the carbon chain of the group, i. is bounded on both sides by carbon atoms.
  • the number of these groups is therefore at least 1 smaller than the number of carbon atoms, and the groups can not be terminal.
  • radicals which are not interrupted by the groups mentioned are preferred.
  • A is a divalent group, especially -C (O) -O-C (O) -, the two terminal carbon atoms of this group are each bonded to different carbon atoms of the Z group.
  • the group of the formula (I) contains more than one group A, the plural groups A may each be bonded to the same and / or preferably to different carbon atoms of the group Z.
  • compositions according to the invention which contain surface-functionalized filler with groups of the formula (I) are particularly suitable as dental materials which are distinguished by improved adhesion to the dental hard material, in particular an improved shear bond strength to dentin and tooth enamel.
  • surface-functionalized fillers can form covalent bonds via the functional groups A with hydroxyapatite and / or collagen of the hard tooth substance.
  • acid groups can react with hydroxyapatite and carboxylic anhydrides or aldehydes with collagen.
  • A is each independently -COOH, -P (O) (OH) 2 , -OP (O) (OH) 2 , -SO 2 OH, -CHO, -NH-C (O) -CHO, -C ( O) -CHO, -C (O) -CH 2 -C (O) -CH 3 or -OC (O) -CH 2 -C (O) -CH 3 .
  • R 1 is C 1 -C 3 alkyl, most preferably methyl.
  • R 2 is particularly preferably C 1 -C 3 -alkylene.
  • Y is particularly preferably an ether or thioether group.
  • Z particularly preferably represents an at least divalent linear or branched aliphatic radical having 2 to 10 carbon atoms which may be interrupted by one or more ether or ester groups and one or more cycloaliphatic groups having at least 3 carbon atoms and / or one or more aromatic groups contain at least 6 carbon atoms, an at least divalent cycloaliphatic radical having at least 3 carbon atoms or an at least bivalent aromatic radical having at least 6 carbon atoms.
  • each A is independently -P (O) (OH) 2 , -OP (O) (OH) 2 , -CHO or -NH-C (O) -CHO.
  • a is 1 or 2.
  • alkyl and alkylene radicals are preferably linear groups.
  • compositions of the invention contain at least one filler whose surface is functionalized.
  • Suitable fillers are, in particular, inorganic particles and fibers.
  • Particulate materials having an average particle size of from 1 nm to 10 ⁇ m, preferably from 5 nm to 5 ⁇ m, are preferably used as the filler.
  • the term mean particle size here refers to the volume average.
  • Preferred fillers are inorganic, preferably amorphous materials. Particular preference is given to monodisperse, nanoparticulate fillers, preferably based on SiO 2 , such as fumed silica or precipitated silica, oxides of the elements Zr, Ti, Al, Y, La, Ce and / or Yb and their mixed oxides with SiO 2 . It is preferred that the filler has an average particle size from 5 to 200 nm, more preferably 10 to 100 nm, most preferably 10 to 50 nm.
  • A is preferably each independently -COOH, -P (O) (OR 3 ) 2 , -OP (O) (OR 3 ) 2 , -SO 2 OH, -CHO, -NH-C (O) -CHO or - OC (O) -CH 2 -C (O) -CH 3 .
  • X is particularly preferably halogen or C 1 -C 3 -alkoxy, in particular Cl, methoxy, ethoxy or n-propoxy, most preferably methoxy.
  • each A is independently -P (O) (OR 3 ) 2 , -OP (O) (OR 3 ) 2 , -CHO or -NH-C (O) -CHO.
  • R 3 is H or C 1 -C 3 alkoxy, most preferably H, methoxy or ethoxy.
  • silanes according to formula (II) include:
  • compositions which have at least one filler surface-functionalized with groups of the formula (I) in which the groups of the formula (I) derive from one of the abovementioned silanes of the formula (II) are particularly preferred according to the invention.
  • silanes according to formula (II) can be prepared analogously to from silicon chemistry (for example MA Brook, Silicon in Organic, Organometallic, and Polymer Chemistry, John Wiley & Sons Inc., New York, etc. 1999 ) and organic chemistry (for example W. Walter, W. Franke, Bayer-Walter Textbook of Organic Chemistry, 24th ed., S. Hirzel Verlag, Stuttgart and Stuttgart 2004 ; Author collective, Organikum, 21st edition, Wiley-VCH, Weinheim etc. 2001 ) produce known methods.
  • silicon chemistry for example MA Brook, Silicon in Organic, Organometallic, and Polymer Chemistry, John Wiley & Sons Inc., New York, etc. 1999
  • organic chemistry for example W. Walter, W. Franke, Bayer-Walter Textbook of Organic Chemistry, 24th ed., S. Hirzel Verlag, Stuttgart and Stuttgart 2004 ; Author collective, Organikum, 21st edition, Wiley-VCH, Weinheim etc. 2001
  • a synthesis method is, for example, the linking of Si-H and vinyl group-containing compounds by hydrosilylation:
  • Surface-modified fillers with groups of the formula (I) are obtainable in particular by reacting the filler with a silane.
  • siliceous fillers stable siloxane bonds are formed Silanol groups on the surface of the filler and silicon atoms of the silane.
  • a filler surface-modified with groups of formula (I) is obtained by reacting the filler with at least one silane of formula (II).
  • the filler in a first step, is reacted with a silane which is a precursor of a silane of the formula (II), and the resulting product is subsequently reacted in one or more steps to form a filler surface-functionalized with groups of the formula (I) , Silanes which are a precursor of a silane of the formula (II) according to one of the methods discussed above are particularly preferred.
  • silylation of the filler with trimethoxysilane subsequent reaction of the product with allyl alcohol and final oxidation of the primary OH group to the aldehyde group.
  • an aldehyde group-containing filler silanization of the filler with 3-isocyanatopropyltriethoxysilane and subsequent reaction of the product with 4-hydroxymethylbenzaldehyde.
  • the phosphonic acid group is then released by hydrolysis of the phosphonic acid ester group.
  • this is shown in the following scheme:
  • a surface-functionalized with groups of the formula (I) filler by reacting a filler with a silane can be done in different ways.
  • a liquid silane can be mixed directly with filler and then dried to remove condensation products.
  • a filler is dispersed in a solution of the silane in a suitable solvent.
  • the interaction of the silane with the filler surface can be influenced by the polarity of the solvent. It has been found that such a method leads to a better wetting of the filler surface and is particularly advantageous for very finely divided fillers having a specific surface area greater than 30 m 2 / g, in particular greater than 40 m 2 / g.
  • Suitable solvents are C 1 -C 6 -alkanols, such as ethanol or isopropanol, cyclic ethers, such as tetrahydrofuran or dioxane, aliphatic esters, such as ethyl acetate or butyl acetate, aliphatic hydrocarbons, such as hexane, and cycloaliphatic hydrocarbons, such as cyclohexane.
  • C 1 -C 6 -alkanols such as ethanol or isopropanol
  • cyclic ethers such as tetrahydrofuran or dioxane
  • aliphatic esters such as ethyl acetate or butyl acetate
  • aliphatic hydrocarbons such as hexane
  • cycloaliphatic hydrocarbons such as cyclohexane.
  • the filler After completion of the reaction, the filler is separated, optionally washed once or more times with the same and / or another solvent, optionally a heat treatment subjected if necessary, washed again and then dried. After the surface functionalization, the filler is optionally ground. This can be advantageous in particular with fillers which tend to form agglomerates.
  • organosol refers in particular to colloidal suspensions in which the continuous phase is an organic compound, in particular an organic solvent or a polymerizable monomer which is liquid at room temperature. Examples of suitable polymerizable monomers are as described below.
  • the degree of surface functionalization depends, inter alia, on the filler or surface area of the filler, the amount and structure of the silane, the reaction time, the temperature, the type of catalyst used and the filler pretreatment , such as a pre-drying.
  • the various influencing factors are generally very well studied, especially in the silanization of SiO 2 (cf. EP Plueddemann, "Silane Coupling Agents", Plenary Press, 2nd ed., New York and London, 1991 ; A. Guillet, Macromol. Symp. 194 (2003) 63 ).
  • surface-functionalized fillers are preferred with groups of the formula (I) which can be obtained by using a filler with at least 0.01 mmol, preferably 0.1-5 mmol, more preferably 0.5 to 2 mmol of a suitable silane per gram the filler is reacted.
  • silanes of the formula (II) and silanes which are a precursor of a silane of the formula (II), as described above, are particularly preferred.
  • the degree of surface functionalization of the filler surface-functionalized with groups of the formula (I) can be determined, for example, by means of elemental analysis. In the case of groups of the formula (I) which contain phosphorus and / or sulfur, in particular the content of the surface-functionalized filler on one of these elements can be used to determine the degree of functionalization.
  • the filler surface-functionalized with groups of the formula (I) contains at least 0.01 mmol, preferably 0.05-2 mmol, more preferably 0.1-1 mmol, of groups of the formula (I) per gram of the filler.
  • the filler surface-functionalized with groups of the formula (I) is at least 0.01 mmol, preferably 0.05-2 mmol, more preferably 0.1-1 mmol groups of the formula Contains (I) per gram of SiO 2 .
  • the filler surface-functionalized with groups of the formula (I) may additionally be modified with further groups.
  • the term "another group” refers to a group which does not have the formula (I).
  • the filler surface-functionalized with groups of the formula (I) may additionally be modified with polymerizable and / or non-functionalized groups.
  • Preferred polymerizable groups are groups which have at least one (meth) acrylic ester and / or (meth) acrylamide functionality, in particular (meth) acryloyloxyalkylsilyl groups or (meth) acrylamidoalkylsilyl groups.
  • alkyl is preferably understood radicals having 1 to 6, in particular 1 to 3 carbon atoms.
  • Non-functionalized groups are understood to mean those groups which do not have the formula (I) and are not polymerizable.
  • An additional surface modification of the Filler for example, with polymerizable groups, in particular, the incorporability of the filler in the compositions of the invention and the mechanical properties of dental materials prepared therefrom improve.
  • Fillers which have been surface-functionalized with groups of the formula (I) and which are additionally modified with further groups are obtainable in particular by reacting the filler with at least one further silane before, after or together with the surface functionalization with at least one group of the formula (I) ,
  • Another variant consists in carrying out a silanization of the filler with one or more polymerizable and / or non-functionalized further silanes before or after the surface modification of a filler with at least one silane of the formula (II).
  • suitable polymerizable silanes are (meth) acryloyloxyalkyltrialkoxysilanes such as 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyldimethylmethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane or 3-acryloyloxypropyldimethylmethoxysilane.
  • Polymerizable silanes carrying two methacrylate radicals can be easily prepared, for example, by reacting glycerol dimethacrylate with 3-isocyanatopropyltriethoxysilane or 3- (methyldiethoxysilyl) -propylsuccinic anhydride or with glutaric anhydride and then with 3-aminopropyltriethoxysilane.
  • polymerizable (meth) acrylamidoalkyltrialkoxysilanes such as, for example, 3- (N-methacryloylamino) -propyltrimethoxysilane, 3- (N-acryloylamino) -propyltrimethoxysilane, 3- (N-Methacryloylamino) -propyltriethoxysilane, 3- (N-Methacryloyl-N-ethylamino) -propyltrimethoxysilane, 3- (N-Methacryloyl-N-ethyl-amino) -propyltrimethoxysilane, 3- (N-Acryloyl-N -ethyl-amino) -propyltrimethoxysilane, 3- (N-methacryloyl-N-methyl-amino) -propyltrimethoxysilane or 3- (N-acryloyl-N-me
  • compositions according to the invention contain at least one polymerisable monomer.
  • polymerizable monomers are particularly suitable radically polymerizable monomers.
  • radically polymerizable monomers may have one or more radically polymerizable groups.
  • Preferred free-radically polymerizable monomers are liquid monomers which are suitable at room temperature and are suitable as diluent monomers. Preference is given to monomers having a viscosity of 0.01 to 10 Pa ⁇ s at room temperature, in particular mono- or polyfunctional (meth) acrylates.
  • hydrolysis-stable diluent monomers in particular mono (meth) acrylates, such as mesityl methacrylate, 2- (alkoxymethyl) acrylic acids, such as 2- (ethoxymethyl) acrylic acid and 2- (hydroxymethyl) acrylic acid, N-mono-alkyl-substituted acrylamides, such as N Ethylacrylamide or N- (2-hydroxyethyl) acrylamide, N-monoalkyl-substituted methacrylamides such as N-ethylmethacrylamide, N- (2-hydroxyethyl) methacrylamide or N- (5-hydroxypentyl) methacrylamide, N, N-dialkyl substituted acrylamides such as N, N-dimethylacrylamide or N-methyl-N- (2-hydroxyethyl) acrylamide, and N-vinylpyrrolidone.
  • mono (meth) acrylates such as mesityl methacrylate, 2- (alkoxymethyl) acrylic acids,
  • alkyl is preferably understood radicals having 1 to 6, in particular 1 to 3 carbon atoms.
  • further diluent monomers are mono (meth) acrylates, such as, for example, methyl, ethyl, butyl, benzyl, furfuryl or phenyl (meth) acrylate.
  • compositions according to the invention preferably comprise 0 to 50% by weight, preferably 5 to 40% by weight and very particularly preferably 10 to 30% by weight of diluent monomer. These and, unless otherwise indicated, all other percentages are by weight based on the total weight of the composition.
  • compositions according to the invention preferably comprise at least one monomer having 2 or more, in particular 2 to 5, radically polymerizable groups.
  • Monomers having 2 or more polymerizable groups act as crosslinkers, thus increasing the mechanical stability of the cured compositions.
  • Preferred crosslinker monomers are hydrolysis-stable crosslinker monomers, in particular crosslinking pyrrolidones, such as 1,6-bis (3-vinyl-2-pyrrolidonyl) hexane or commercially available bis (meth) acrylamides, such as methylene or ethylenebisacrylamide, N, N'-diethyl 1,3-bis (acrylamido) -propane, 1,3-bis (methacrylamido) -propane, 1,4-bis (acrylamido) -butane, 1,4-bis (acryloyl) -piperazine, 2,6-dimethylene 4-oxa-heptane-1,7-dicarboxylic acid bis (propylamide), 1,6-bis (acrylamido) -2,2,4 (2,4,4) -trimethyl-hexane and N, N ' dimethyl-1,6-bis (acrylamido) hexane.
  • crosslinkers are polyfunctional (meth) acrylates, for example bisphenol A di (meth) acrylate, bis-GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether), UDMA (an addition product of 2-hydroxyethyl methacrylate and 2, 2,4-hexamethylene diisocyanate), di-, tri- or tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, butanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate or 1,12-dodecanediol di (meth) acrylate.
  • polyfunctional (meth) acrylates for example bisphenol A di (meth) acrylate, bis-GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether),
  • compositions which, in addition to the filler surface-functionalized with groups of the formula (I), contain 0 to 45% by weight, preferably 1 to 30% by weight and very particularly preferably 5 to 20% by weight of crosslinking monomer, in particular bis (meth) acrylamide , are particularly preferred according to the invention.
  • the compositions contain at least one acidic radically polymerizable monomer, i. a monomer having one or more acidic groups such as carboxylic anhydride, carboxylic acid, phosphoric acid, dihydrogen phosphate, phosphonic acid and sulfonic acid groups.
  • acidic groups are carboxylic acid, phosphoric acid and phosphonic acid groups.
  • Such monomers are suitable as adhesive monomers, in particular for enamel / dentin adhesives or self-adhesive composites.
  • Particularly preferred acidic monomers are polymerizable acrylate ether phosphonic acids, such as 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid ethyl ester, 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid or 2- [4 - (Dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid 2,4,6-trimethylphenyl ester, (meth) acrylamidoalkylenephosphonic acids or (meth) acrylamidoalkylenebisphosphonic acids.
  • 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid ethyl ester 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid or 2- [4 - (Dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid 2,4,
  • hydrolysis-stable, polymerizable dihydrogen phosphates such as (meth) acrylamidoalkylene phosphates, (meth) acrylamido cycloalkylene phosphates or (meth) acrylamidoaryl dihydrogen phosphates, eg 2- (N-acryloylamino) ethyl dihydrogen phosphate, 2- (N-methacryloylamino) ethyl dihydrogen phosphate, 6- (N-acryloylamino ) hexyl dihydrogen phosphate, 6- (N-methacryloylamino) hexyl dihydrogen phosphate, 4- (N-acryloylamino) phenyl dihydrogen phosphate, 4- (N-methacryloylamino) phenyl dihydrogen phosphate, 1,3-bis (N-acryloylamino) -propan-2-yl dihydrogen phosphat
  • compositions which, in addition to the surface-functionalized with groups of formula (I) filler 1 to 50 wt .-%, preferably 5 to 40 wt .-% and most preferably 10 to 30 wt .-% acidic monomer, in particular acidic monomer with dihydrogen phosphate , Phosphonic acid and / or sulfonic acid groups are particularly preferred according to the invention.
  • the composition according to the invention may preferably contain at least one further filler which is not surface-modified with groups of the formula (I).
  • suitable further fillers are fillers that are not surface-modified, fillers that are surface-modified with polymerizable groups, and fillers that are surface-modified with nonfunctionalized groups.
  • Preferred polymerizable groups are groups which have at least one (meth) acrylic ester and / or (meth) acrylamide functionality, in particular (meth) acryloyloxyalkylsilyl groups or (meth) acrylamidoalkylsilyl groups.
  • alkyl is preferably understood radicals having 1 to 6, in particular 1 to 3 carbon atoms.
  • Non-functionalized groups are understood to mean those groups which do not have the formula (I) and are not polymerizable.
  • Such surface-modified fillers are obtainable in particular by silanization of a filler with suitable silanes.
  • fillers surface-modified with polymerizable groups can be obtained by silanizing a filler with at least one of the above-described polymerizable silanes.
  • composition according to the invention preferably contains surface-functionalized compounds in addition to those having groups of the formula (I) Filler 0 to 40 wt .-%, in particular 1 to 30 wt .-% further filler which is not surface-modified with groups of the formula (I).
  • the compositions according to the invention preferably contain an initiator for the free-radical polymerization, in particular for the photochemically or redox-induced free radical polymerization.
  • suitable initiators for the photopolymerization are benzophenone, benzoin and their derivatives or ⁇ -diketones or derivatives thereof, such as 9,10-phenanthrenequinone, 1-phenyl-propane-1,2-dione, diacetyl or 4,4'-dichlorobenzil.
  • Particularly preferred camphorquinone and 2,2-dimethoxy-2-phenyl-acetophenone and most preferably ⁇ -diketones are used in combination with amines as reducing agents.
  • Preferred amines are 4- (N, N-dimethylamino) benzoic acid esters, N, N-dimethylaminoethyl methacrylate, N, N-dimethyl-sym-xylidine and triethanolamine.
  • acylphosphines e.g. 2,4,6-trimethylbenzoyldiphenyl or bis (2,6-dichlorobenzoyl) -4-N-propylphenylphosphine oxide is particularly suitable.
  • redox initiator combinations e.g. Combinations of benzoyl peroxide with N, N-dimethyl-sym-xylidine or N, N-dimethyl-p-toluidine.
  • redox systems consisting of peroxides and reducing agents, e.g. Ascorbic acid, barbiturates or sulfinic acids, particularly suitable.
  • compositions in addition to the surface-functionalized filler 0.1 to 5.0 wt .-%, preferably 0.2 to 2.0 wt .-% and most preferably 0.2 to 1.0 wt .-% initiator for the radical Polymerization are particularly preferred according to the invention.
  • compositions according to the invention may additionally contain solvents, such as water, ethyl acetate or ethanol, or solvent mixtures.
  • solvents such as water, ethyl acetate or ethanol, or solvent mixtures.
  • hydrolysis-stable solvents such as water or ethanol, or solvent mixtures are preferred.
  • compositions of the invention may contain other additives, in particular stabilizers, flavorings, colorants, microbiocidal agents, fluoride ion donating additives, optical brighteners, plasticizers and UV absorbers.
  • compositions comprising at least one acidic monomer or at least one Crosslinking monomer, in particular at least one acidic monomer and at least one crosslinking monomer or at least one acidic crosslinking monomer.
  • compositions according to the invention are particularly suitable as dental materials, in particular as adhesives, cements, preferably self-adhesive cements such as e.g. Fixing cements, and composites, preferably filling composites.
  • dental materials are characterized by a very good adhesion to the hard tooth substance, i. on enamel and dentin, out.
  • compositions of the present invention cure to form highly crosslinked polymer networks that have little or no swelling in water.
  • the invention also relates to a surface-functionalized filler as defined above.
  • the invention further relates to a process for the preparation of a composition or of a surface-functionalized filler according to the invention in which the filler is reacted with at least one silane and the resultant surface-functionalized filler is mixed with the further constituents of the composition.
  • Preferred embodiments of the reaction of the filler with at least one silane are as described above.
  • the invention also relates to the use of a filler surface-functionalized with groups of the formula (I) for producing a dental material, in particular an adhesive or cement.
  • acrolein Under argon, 0.605 g (10.8 mmol) of acrolein and a spatula tip of hydroquinone were placed in the flask. At 0 to 5 ° C then 75.3 g of the organosol produced in the 1st stage were added dropwise within 11 h. The ice bath was removed and the dispersion was stirred for 1 week at room temperature. In the resulting organosol no acrolein was present. The product contained about 58% aldehyde groups, based on the used trialkoxysilane. The ignition residue of the slightly viscous, cloudy and thixotropic organosol was 7.1% SiO 2 .
  • the powder was dispersed in 50 g of ethanol, centrifuged, finally dispersed in cyclohexane and again centrifuged off.
  • the powder obtained was dried on a rotary evaporator at 8 ⁇ 10 -2 mbar.
  • the occupancy with mercapto groups was 0.12 mmol / g SiO 2 and was determined by the sulfur content (0.38 wt .-%, elemental analysis) of the sample.
  • Aerosil 200 25.0 g of Aerosil 200 were suspended in 750 g of cyclohexane. Then, 13.6 g (41.4 mmol) of diethylphosphorylethyltriethoxysilane and 3.68 g (62.25 mmol) of n-propylamine were added. The mixture was stirred at 70 ° C for 30 hours. The solvent was removed at 40 ° C on a rotary evaporator and the product dried for 3 days at 50 ° C in a drying oven. The powder was then washed for washing in 150 ml of ethanol and separated by pressure filtration (0.45 microns) from the solvent. The powder was again washed analogously with ethanol and then once with cyclohexane.
  • the functionalized silane occupancy was 0.66 mmol / g SiO 2 and was determined by the phosphorus content (1.78 wt%, elemental analysis) of the sample.
  • silanized Aerosil 200 from the 1st stage were suspended in 460 g of hydrochloric acid (32 wt .-%) and heated for 46 h under reflux. Then, the hydrochloric acid solution was removed in vacuo at 40 ° C and the powder dried for 3 days in a drying oven at 50 ° C. The modified particles were then redispersed in 150 ml of water and filtered by pressure filtration (0.45 ⁇ m). The process was repeated twice more and then dried the powder for 3 days in a drying oven at 50 ° C. The residue on ignition was 96.0% by weight.
  • the functionalized silane occupancy was 0.58 mmol / g SiO 2 and was determined by the phosphorus content (1.85 wt.%, Elemental analysis) of the sample.
  • the particles were dispersed in 150 ml of ethanol and filtered by pressure filtration (0.45 ⁇ m), dispersed a second time in ethanol and filtered and finally dispersed once more in 150 ml of cyclohexane and filtered off.
  • the powder was dried in a drying oven at 50 ° C for 3 days. The residue on ignition was 94.8% by weight.
  • IR spectroscopy revealed the presence of methacrylate groups by the appearance of a new band at 1636 cm -1 .
  • the powder was again washed analogously with ethanol and then once with 50 ml of cyclohexane. It is then dried again for 3 days at 50 ° C in a drying oven.
  • the functionalized silane occupancy was 0.11 mmol / g SiO 2 and was determined by the phosphorus content (0.32% by weight, elemental analysis) of the sample.
  • Adhesives A according to the invention
  • B comparative example
  • Bovine teeth were embedded in plastic cylinders in such a way that the dentin or tooth enamel and the plastic were in one plane.
  • a layer of adhesive of the above formulation was rubbed onto the surface of the dentin for 30 s with a microbrush, slightly blown with an air blower and exposed for 20 s to a photopolymerization lamp Astralis 7 (Ivoclar Vivadent AG).
  • the filling composite Tetric® Ceram was applied to the adhesive layer (Icoclar Vivadent AG) applied and cured for 40 s with the lamp Astralis 7.
  • the test specimens were stored in water at 37 ° C.

Landscapes

  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Dental Preparations (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP08000956A 2008-01-18 2008-01-18 Matériaux dentaires dotés d'agents de remplissage à surface fonctionnalisée Active EP2080503B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP08000956A EP2080503B1 (fr) 2008-01-18 2008-01-18 Matériaux dentaires dotés d'agents de remplissage à surface fonctionnalisée
AT08000956T ATE524154T1 (de) 2008-01-18 2008-01-18 Dentalmaterialien mit oberflächenfunktionalisierten füllstoffen
US12/275,700 US20090186960A1 (en) 2008-01-18 2008-11-21 Dental materials with surface-functionalized fillers
JP2008334466A JP5308809B2 (ja) 2008-01-18 2008-12-26 表面官能化充填材を含む歯科材料

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP08000956A EP2080503B1 (fr) 2008-01-18 2008-01-18 Matériaux dentaires dotés d'agents de remplissage à surface fonctionnalisée

Publications (2)

Publication Number Publication Date
EP2080503A1 true EP2080503A1 (fr) 2009-07-22
EP2080503B1 EP2080503B1 (fr) 2011-09-14

Family

ID=39342752

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08000956A Active EP2080503B1 (fr) 2008-01-18 2008-01-18 Matériaux dentaires dotés d'agents de remplissage à surface fonctionnalisée

Country Status (4)

Country Link
US (1) US20090186960A1 (fr)
EP (1) EP2080503B1 (fr)
JP (1) JP5308809B2 (fr)
AT (1) ATE524154T1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005019600A1 (de) * 2005-04-27 2006-11-09 Ivoclar Vivadent Ag Oberflächenmodifizierte Füllstoffe
JP5914071B2 (ja) * 2012-03-16 2016-05-11 株式会社トクヤマデンタル 歯科用接着性組成物
US9303149B2 (en) * 2012-06-21 2016-04-05 Prc-Desoto International, Inc. Adhesion promoting adducts containing metal ligands, compositions thereof, and uses thereof
JP6147610B2 (ja) * 2013-08-27 2017-06-14 株式会社トクヤマデンタル 歯科用接着性組成物
US9328275B2 (en) 2014-03-07 2016-05-03 Prc Desoto International, Inc. Phosphine-catalyzed, michael addition-curable sulfur-containing polymer compositions
JP6279391B2 (ja) * 2014-03-31 2018-02-14 株式会社松風 高靭性歯質接着性シランカップリング剤およびそれを含む歯科用組成物
JP6279392B2 (ja) * 2014-03-31 2018-02-14 株式会社松風 機能性複合微粒子を含む高靭性歯科用硬化性組成物
JP6684173B2 (ja) * 2016-06-30 2020-04-22 株式会社ジーシー 歯科用組成物
US12064985B2 (en) * 2021-05-25 2024-08-20 Canon Kabushiki Kaisha Active energy ray-curable liquid composition, recording method, and recording apparatus

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2405578A1 (de) 1974-02-06 1975-08-14 Kulzer & Co Gmbh Polymerisierbares bindemittel enthaltender dentalwerkstoff und daraus hergestellte zaehne und zahnersatzteile
GB1488403A (en) 1974-01-23 1977-10-12 Perdent Gmbh Dental material
US4220582A (en) 1979-01-03 1980-09-02 Lee Pharmaceuticals Dental restorative compositions of improved X-ray opacity
DE3247800A1 (de) 1981-12-23 1983-07-07 Tokuyama Soda K.K., Tokuyama, Yamaguchi Amorphe, kugelfoermige anorganische verbindungen, verfahren zu ihrer herstellung und ihre verwendung
DE4029230A1 (de) 1990-09-14 1992-03-19 Ivoclar Ag Polymerisierbarer dentalwerkstoff
US5367002A (en) 1992-02-06 1994-11-22 Dentsply Research & Development Corp. Dental composition and method
DE4323143C1 (de) 1993-07-10 1994-12-01 Schott Glaswerke Verwendung eines Glases als bariumfreies Dentalglas mit guter Röntgenabsorption
WO1998013008A1 (fr) 1996-09-27 1998-04-02 Southwest Research Institute Compositions et methodes a base d'oxydes metalliques
US5871360A (en) 1996-12-31 1999-02-16 Gc Corporation Method for restoration of a cavity of a tooth using a resin reinforced type glass ionomer cement
WO2000069392A1 (fr) 1999-05-19 2000-11-23 Southwest Research Institute Materiaux composites transparents ou translucides a grande resistance mecanique, fabriques a partir de nanoparticules d'oxyde de zirconium
DE10018405A1 (de) 2000-04-13 2001-10-25 Fraunhofer Ges Forschung Sphärische oxidische Partikel und deren Verwendung
US6387981B1 (en) 1999-10-28 2002-05-14 3M Innovative Properties Company Radiopaque dental materials with nano-sized particles
US20020065337A1 (en) 1997-10-03 2002-05-30 Dentsply Detrey Gmbh. Dental materials having a nanoscale filler
US6417244B1 (en) 1993-04-13 2002-07-09 Southwest Research Institute Metal oxide compositions and methods
WO2003070198A1 (fr) * 2002-02-15 2003-08-28 Dentsply International Inc. Composition dentaire adhesive
US20030175217A1 (en) * 2000-06-16 2003-09-18 Christian Kropf Thixotropic oral and dental care agents
DE102004022566A1 (de) 2004-05-07 2005-12-01 Schott Ag Mit funktionellen Gruppen homogen beschichtete Pulverteilchen, ein Verfahren zu deren Herstellung und ihre Verwendung
US20060247329A1 (en) * 2005-04-27 2006-11-02 Ivoclar Vivadent Ag Surface-modified fillers
FR2889704A1 (fr) * 2005-08-12 2007-02-16 Rhodia Chimie Sa Particules minerales de surface modifiee par des composes porteurs de fonctions xanthate et silane.

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816550A (en) * 1972-10-02 1974-06-11 Union Carbide Corp Catalytic process for hydration of olefins
US4463114A (en) * 1982-03-31 1984-07-31 Minnesota Mining And Manufacturing Company Antistatic films
WO1984000375A1 (fr) * 1982-07-14 1984-02-02 Battelle Development Corp Procede de production de revetements de resines reticulees sur des substrats
US4451343A (en) * 1983-09-02 1984-05-29 The Standard Oil Company Photo-initiators for decarboxylation reactions
US5736249A (en) * 1994-08-16 1998-04-07 Decora, Incorporated Non-stick polymer-coated articles of manufacture
JP2001089128A (ja) * 1998-04-10 2001-04-03 Asahi Glass Co Ltd 球状シリカ粒子の製造方法
US6765037B2 (en) * 2001-11-03 2004-07-20 Dymax Corporation Photopolymerizable epoxy composition
DE10304849A1 (de) * 2003-02-06 2004-08-19 Institut für Neue Materialien gemeinnützige Gesellschaft mit beschränkter Haftung Chemomechanische Herstellung von Funktionskolloiden

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1488403A (en) 1974-01-23 1977-10-12 Perdent Gmbh Dental material
DE2405578A1 (de) 1974-02-06 1975-08-14 Kulzer & Co Gmbh Polymerisierbares bindemittel enthaltender dentalwerkstoff und daraus hergestellte zaehne und zahnersatzteile
US4220582A (en) 1979-01-03 1980-09-02 Lee Pharmaceuticals Dental restorative compositions of improved X-ray opacity
DE3247800A1 (de) 1981-12-23 1983-07-07 Tokuyama Soda K.K., Tokuyama, Yamaguchi Amorphe, kugelfoermige anorganische verbindungen, verfahren zu ihrer herstellung und ihre verwendung
DE4029230A1 (de) 1990-09-14 1992-03-19 Ivoclar Ag Polymerisierbarer dentalwerkstoff
US5367002A (en) 1992-02-06 1994-11-22 Dentsply Research & Development Corp. Dental composition and method
US6417244B1 (en) 1993-04-13 2002-07-09 Southwest Research Institute Metal oxide compositions and methods
DE4323143C1 (de) 1993-07-10 1994-12-01 Schott Glaswerke Verwendung eines Glases als bariumfreies Dentalglas mit guter Röntgenabsorption
WO1998013008A1 (fr) 1996-09-27 1998-04-02 Southwest Research Institute Compositions et methodes a base d'oxydes metalliques
US5871360A (en) 1996-12-31 1999-02-16 Gc Corporation Method for restoration of a cavity of a tooth using a resin reinforced type glass ionomer cement
US20020065337A1 (en) 1997-10-03 2002-05-30 Dentsply Detrey Gmbh. Dental materials having a nanoscale filler
WO2000069392A1 (fr) 1999-05-19 2000-11-23 Southwest Research Institute Materiaux composites transparents ou translucides a grande resistance mecanique, fabriques a partir de nanoparticules d'oxyde de zirconium
US6387981B1 (en) 1999-10-28 2002-05-14 3M Innovative Properties Company Radiopaque dental materials with nano-sized particles
DE10018405A1 (de) 2000-04-13 2001-10-25 Fraunhofer Ges Forschung Sphärische oxidische Partikel und deren Verwendung
US20030175217A1 (en) * 2000-06-16 2003-09-18 Christian Kropf Thixotropic oral and dental care agents
WO2003070198A1 (fr) * 2002-02-15 2003-08-28 Dentsply International Inc. Composition dentaire adhesive
DE102004022566A1 (de) 2004-05-07 2005-12-01 Schott Ag Mit funktionellen Gruppen homogen beschichtete Pulverteilchen, ein Verfahren zu deren Herstellung und ihre Verwendung
US20060247329A1 (en) * 2005-04-27 2006-11-02 Ivoclar Vivadent Ag Surface-modified fillers
FR2889704A1 (fr) * 2005-08-12 2007-02-16 Rhodia Chimie Sa Particules minerales de surface modifiee par des composes porteurs de fonctions xanthate et silane.

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
G. MACBEATH; S. L. SCHREIBER, SCIENCE, vol. 289, 2000, pages 1760 - 1763
M.T. DULAY ET AL., ANALYT. CHEM., vol. 77, 2005, pages 4604 - 4610
S. B. LEE ET AL., SCIENCE, vol. 296, 2002, pages 2198 - 2200
W. CLARKE ET AL., J. CHROMATOGRAPHY A, vol. 888, 2000, pages 13 - 22

Also Published As

Publication number Publication date
JP2009167186A (ja) 2009-07-30
ATE524154T1 (de) 2011-09-15
US20090186960A1 (en) 2009-07-23
EP2080503B1 (fr) 2011-09-14
JP5308809B2 (ja) 2013-10-09

Similar Documents

Publication Publication Date Title
EP2080503B1 (fr) Matériaux dentaires dotés d'agents de remplissage à surface fonctionnalisée
EP1716836B1 (fr) Charges à surface modifiée
DE68908087T2 (de) Dentales Restaurationsmaterial.
DE19903177C2 (de) Dentalmaterialien auf der Basis von Polysiloxanen
EP3120827B1 (fr) Matieres dentaires adhesive presentant des polymeres adhesifs tres acides
EP2103296B1 (fr) Matière de remplissage de verre revêtue de polymère et destinée à être utilisée dans des matières dentaires
EP3020361A1 (fr) Utilisation de compositions a durcissement radicalaire dans un procede de fabrication generative
EP3020360B1 (fr) Compositions dentaires à durcissement radicalaire
EP3166569B1 (fr) Composite à structure réticulée contrôlée
CN111228124B (zh) 快速固化和低收缩应力的可光聚合牙科复合材料
WO2016177680A1 (fr) Materiaux dentaires durcissables par polymérisation par transfert de chaîne
JP7094165B2 (ja) シランベースの移動試薬を含むポリマー材料
EP2004131B1 (fr) Matériaux dentaires contenant des cocondensats d'acide silicique hydrophobes et nanoparticulaires et utilisation desdits matériaux
EP3782599A1 (fr) Composition dentaire polymérisable à base de silanes condensés
EP2289483A1 (fr) Utilisation de polyéthers macrocycliques polymérisables et de polyéthers macrocycliques hétéroanalogues dans des matériaux dentaires
EP3868767B1 (fr) Photoinitiateurs absorbant les ondes longues
EP4039220A1 (fr) Matières dentaires à base de dérivés polymerisables de thiouree
WO2015139811A1 (fr) Mélange de monomères pour la préparation de matériaux dentaires
EP4356893A1 (fr) Ciments composites auto-adhésifs stables au stockage présentant une bonne transparence et une bonne radio-opacité
EP3932383B1 (fr) Composite à contrainte de retrait de polymérisation réduite
EP2489344A1 (fr) Matériau dentaire comprenant une substance anti-microbienne
EP2883528A1 (fr) Matériaux dentaires à base d'alcynes et d'azides polymérisables

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

17P Request for examination filed

Effective date: 20100121

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20100429

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

RIN1 Information on inventor provided before grant (corrected)

Inventor name: RHEINBERGER, VOLKER, DR.

Inventor name: ANGERMANN, JOERG, DR.

Inventor name: MOSZNER, NORBERT, PROF. DR.

Inventor name: KLAPDOHR, SIMONE, DR.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: CH

Ref legal event code: NV

Representative=s name: KELLER & PARTNER PATENTANWAELTE AG

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502008004833

Country of ref document: DE

Effective date: 20111110

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111214

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111215

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120114

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120116

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

BERE Be: lapsed

Owner name: IVOCLAR VIVADENT AG

Effective date: 20120131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

26N No opposition filed

Effective date: 20120615

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502008004833

Country of ref document: DE

Effective date: 20120615

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111225

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 524154

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130118

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080118

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCAR

Free format text: NEW ADDRESS: EIGERSTRASSE 2 POSTFACH, 3000 BERN 14 (CH)

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20161228

Year of fee payment: 10

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180118

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 502008004833

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: A61K0006083000

Ipc: A61K0006887000

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: IVOCLAR VIVADENT AG, LI

Free format text: FORMER OWNER: IVOCLAR VIVADENT AG, LI

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230607

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231219

Year of fee payment: 17

Ref country code: GB

Payment date: 20240108

Year of fee payment: 17

Ref country code: CH

Payment date: 20240202

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240111

Year of fee payment: 17